JP6988332B2 - Three-dimensional molded film and resin molded products - Google Patents

Description

The present invention relates to a three-dimensional molded film and a resin molded product.

For the purpose of surface protection and further decoration of the surface of resin molded products conventionally used for vehicle interior / exterior parts, building material interior materials, home appliance housings, etc., and organic glass used as a substitute material for inorganic glass. A technique for laminating a three-dimensional molded film is known for the purpose of laminating. In such a technique, roughly classified, the surface protective layer is laminated on the supporting base material of the three-dimensional molded film so as to be located on the outermost surface, and the molding resin is laminated on the supporting base material side. , A laminated three-dimensional molded film used to incorporate the supporting base material into the resin molded product, and a surface protective layer laminated directly on the supporting base material or via a release layer provided as necessary. There are two types of transfer-type three-dimensional molded films that do not leave a supporting base material in the resin molded product by laminating the molding resin on the opposite side of the supporting base material and then peeling off the supporting base material. , It is used properly according to the shape of the resin molded product and the desired function.

By the way, as the protective layer of the three-dimensional molded film, from the viewpoint of giving excellent surface physical properties to the resin molded product, it is chemically crosslinked and cured by irradiating it with ionizing radiation typified by ultraviolet rays or electron beams. It is said that it is preferable to use a resin composition containing an ionizing radiation curable resin. When such a resin is used, it is roughly classified into a case where it is already cured by ionizing radiation in the state of a three-dimensional molded film and a case where it is cured after being made into a resin molded product by molding processing. From the viewpoint of increasing productivity, the former technique is considered to be preferable, and for example, the technique described in Patent Document 1 has been proposed.

Japanese Unexamined Patent Publication No. 2012-56236

In the three-dimensional molded film used for the above-mentioned applications, high scratch resistance is required on the surface, and for example, by using the technique disclosed in Patent Document 1, the scratch resistance can be improved.

However, as a result of repeated studies by the present inventors, although the scratch resistance of the three-dimensional molded film can be improved by the technique disclosed in Patent Document 1, it is severe because it is used outdoors for a long period of time. Under such circumstances, a new problem regarding durability has been found in which the protective layer provided on the three-dimensional molded film is peeled off.

Under such circumstances, it is a main object of the present invention to provide a three-dimensional molded film having both excellent scratch resistance and excellent durability. Another object of the present invention is to provide a method for manufacturing a resin molded product using the three-dimensional molded film.

The present inventors have made diligent studies to solve the above problems. As a result, the first protective layer and the second protective layer are provided in this order, and the first protective layer is formed of a cured product of an ionizing radiation curable resin composition containing a caprolactone-based urethane (meth) acrylate. The second protective layer is formed of a cured product of an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate, and these layers are resin-molded so that the first protective layer is the outermost surface layer. It has been found that a three-dimensional molded film that can be laminated on a product has both excellent scratch resistance and excellent durability. The present invention has been completed by further studies based on such findings.

That is, the present invention provides the inventions of the following aspects.
Item 1. It has at least a base material, a first protective layer, and a second protective layer in this order, and the base material can be peeled off from the first protective layer.
The first protective layer is formed of a cured product of an ionizing radiation curable resin composition containing caprolactone-based urethane (meth) acrylate.
The second protective layer is a three-dimensional molded film formed of a cured product of an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate.
Item 2. It has at least a first protective layer, a second protective layer, and a base material in this order.
The first protective layer is formed of a cured product of an ionizing radiation curable resin composition containing caprolactone-based urethane (meth) acrylate.
The second protective layer is a three-dimensional molded film formed of a cured product of an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate.
Item 3. Item 3. The three-dimensional molded film according to Item 1 or 2, wherein the thickness of the first protective layer and the second protective layer is 1 to 10 μm, respectively.
Item 4. Item 3. The three-dimensional molded film according to any one of Items 1 to 3, wherein at least one of the first protective layer and the second protective layer contains at least one of an ultraviolet absorber and a light stabilizer.
Item 5. Item 6. The three-dimensional molded film according to any one of Items 1 to 4, wherein the polycarbonate (meth) acrylate has a weight average molecular weight of 1000 to 50000.
Item 6. At least a molding resin layer, a second protective layer, and a first protective layer are provided in this order.
The first protective layer is formed of a cured product of an ionizing radiation curable resin composition containing caprolactone-based urethane (meth) acrylate.
The second protective layer is a resin molded product formed of a cured product of an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate.

According to the present invention, it is possible to provide a three-dimensional molded film having both excellent scratch resistance and excellent durability. Further, according to the present invention, it is also possible to provide a resin molded product using the three-dimensional molded film.

It is a schematic sectional drawing of an example (first aspect) of the three-dimensional molded film of this invention. It is a schematic sectional drawing of an example (first aspect) of the three-dimensional molded film of this invention. FIG. 3 is a schematic cross-sectional view of a resin molded product with a transfer substrate obtained by using the three-dimensional molded film shown in FIG. 2. FIG. 3 is a schematic cross-sectional view of a resin molded product obtained by peeling a transfer base material from the resin molded product with a transfer base material shown in FIG. It is a schematic sectional drawing of an example (second aspect) of the three-dimensional molded film of this invention. It is a schematic sectional drawing of an example (second aspect) of the three-dimensional molded film of this invention. 6 is a schematic cross-sectional view of a resin molded product obtained by using the three-dimensional molded film shown in FIG.

1. 1. Three-dimensional molded film The three-dimensional molded film according to the first aspect of the present invention has a base material, the first protective layer, and the second protective layer in this order, and the base material has the first protection. The first protective layer can be peeled off from the layer, the first protective layer is formed of a cured product of an ionizing radiation curable resin composition containing a caprolactone-based urethane (meth) acrylate, and the second protective layer is polycarbonate (meth). It is characterized in that it is formed of a cured product of an ionizing radiation curable resin composition containing acrylate. Further, the three-dimensional molded film of the second aspect of the present invention has at least the first protective layer, the second protective layer, and the base material in this order, and the first protective layer is: The second protective layer is formed of a cured product of an ionizing radiation curable resin composition containing a caprolactone-based urethane (meth) acrylate, and the second protective layer is formed of a cured product of the ionizing radiation curable resin composition containing a polycarbonate (meth) acrylate. It is characterized by being formed. That is, in the present invention, the three-dimensional molded film includes at least a first protective layer and a second protective layer, and the first protective layer is ionized and radiation-curable containing a caprolactone-based urethane (meth) acrylate. It is formed of a cured product of the resin composition, and the second protective layer is characterized by being formed of a cured product of an ionizing radiation curable resin composition containing a polycarbonate (meth) acrylate. The three-dimensional molded film (first aspect and second aspect) of the present invention has such a structure, so that it has excellent scratch resistance and excellent durability (particularly, it is irradiated with ultraviolet rays for a long period of time. (Weather resistance to the environment where dew condensation occurs) can be exhibited. Hereinafter, the three-dimensional molded film of the present invention will be described in detail.

In this specification, the numerical range indicated by "~" means "greater than or equal to" and "less than or equal to". For example, the notation of 2 to 15 mm means 2 mm or more and 15 mm or less. Further, as described later, the three-dimensional molded film of the present invention may not have a decorative layer or the like, and may be transparent, for example. Further, "(meth) acrylate" means "acrylate or methacrylate", and other similar substances have the same meaning.

Laminated Structure of Three-Dimensional Molded Film As shown in FIGS. 1, 2 and 5, 6, the three-dimensional molded film of the present invention includes at least a first protective layer 1 and a second protective layer 2. In the three-dimensional molded film of the present invention, the first protective layer 1 is located on the surface side (that is, the side opposite to the side laminated with the molding resin layer), and the three-dimensional molded film of the present invention is resin-molded. When laminated on the product, the first protective layer 1 becomes the outermost surface of the resin molded product.

The three-dimensional molded film of the first aspect and the second aspect of the present invention has a base material 3 for the purpose of enhancing the shape retention of the three-dimensional molded film. As will be described later, in the case of producing a resin molded product using the three-dimensional molded film of the present invention, as shown in FIGS. 1 and 2, the base material 3 of the three-dimensional molded film is used for transfer, and the said after transfer. The base material 3 (hereinafter, may be referred to as a transfer base material 3a) is peeled off, and the transfer type three-dimensional molded film of the first aspect, which is not included in the resin molded product, can be used, and FIG. As shown in FIGS. ..

Further, as shown in FIGS. 1, 2 and 5, 6, the three-dimensional molded film of the present invention may be provided with a primer layer 4, a decorative layer 5, a transparent resin layer 6, and the like, if necessary. .. The primer layer 4 can be provided at least one of these layers for the purpose of improving the adhesion between the layers of the second protective layer 2, the base material 3, the decorative layer 5, the transparent resin layer 6, and the like. .. Further, the decorative layer 5 is opposite to the base material 3 of the second protective layer 2 if it is the transfer type three-dimensional molded film of FIGS. 1 and 2 for the purpose of imparting decorativeness to the three-dimensional molded film. On the side, in the case of the laminated three-dimensional molded film of FIGS. 5 and 6, it can be provided between the base material 3 and the second protective layer 2. Further, the transparent resin layer 6 can be used with the base material 3 of the second protective layer 2 in the case of the transfer-type three-dimensional molded film of FIGS. 1 and 2 for the purpose of improving the moldability of the three-dimensional molded film. Can be provided on the opposite side between the base material 3 and the second protective layer 2 in the case of the laminated three-dimensional molded film of FIGS. 5 and 6.

Further, although not shown, in the transfer type three-dimensional molded film of the first aspect, the base material 3 is required for the purpose of improving the releasability of the base material 3 from the first protective layer 1. A release layer (not shown) may be provided between the first protective layer 1 and the first protective layer 1. Further, in the three-dimensional molded film of the second aspect, between the base material 3 and the primer layer 4 for the purpose of suppressing color change and variation of the base material 3 contained in the resin molded product. Alternatively, a concealing layer (not shown) may be provided on the back surface of the decorative layer 5 (molding resin layer 8 side) or the like, if necessary. Further, the outermost surface on the molding resin layer 8 side (the surface opposite to the base material 3 in the three-dimensional molded film of the first aspect, and the base material 3 in the three-dimensional molded film of the second aspect). An adhesive layer 7 or the like may be provided on the side surface).

As described above, in the case of producing a resin molded product using the three-dimensional molded film of the present invention, the first aspect in which the base material 3 (transfer base material 3a) of the three-dimensional molded film is not included in the resin molded product. The transfer type three-dimensional molded film of the above, or the three-dimensional molded film of the second aspect in which the base material 3 (layering base material 3b) of the three-dimensional molded film is included in the resin molded product can be used. That is, in the transfer-type three-dimensional molded film of the first aspect, as shown in FIGS. 3 and 4, the molding resin layer 8 is formed on the side opposite to the base material 3, for example, for transfer as shown in FIG. Since the base material 3 is peeled off after the resin molded product with the base material is obtained, the base material 3 is not included in the resin molded product as shown in FIG. On the other hand, in the three-dimensional molded film of the second aspect, the base material 3 is included in the resin molded product as shown in FIG. 7 by forming the molding resin layer 8 on the base material 3 side. The layers transferred using the transfer base material 3a (that is, the first protective layer 1, the second protective layer 2, the primer layer 4, the decorative layer 5, the transparent resin layer 6, the concealing layer, and the adhesive layer 7) are transferred. Etc.) are collectively referred to as a transfer layer 10 (see FIGS. 5 to 8).

As a laminated structure of the three-dimensional molded film of the first aspect of the present invention, a laminated structure in which a second protective layer 2 / a first protective layer 1 / a base material is laminated in this order; a decorative layer / a second protective layer. 2 / Laminated structure in which the first protective layer 1 / base material is laminated in this order; Decorative layer / Primer layer / Second protective layer 2 / Laminated structure in which the first protective layer 1 / base material is laminated in this order Adhesive layer 7 / decorative layer / primer layer / second protective layer 2 / first protective layer 1 / base material laminated in this order; decorative layer / primer layer / transparent resin layer / primer layer / first 2 protective layer 2 / first protective layer 1 / laminated structure in which base materials are laminated in this order; concealing layer / decorative layer / primer layer / transparent resin layer / primer layer / second protective layer 2 / first Laminated structure in which the protective layer 1 / base material is laminated in this order; the adhesive layer 7 / decorative layer / primer layer / transparent resin layer / primer layer / second protective layer 2 / first protective layer 1 / base material is this. Laminated structure in which the decorative layer / primer layer / transparent resin layer / primer layer / second protective layer 2 / first protective layer 1 / release layer / base material are laminated in this order, etc. Can be mentioned. In FIG. 1, as one aspect of the laminated structure of the three-dimensional molded film of the first aspect, the adhesive layer 7 / decorative layer / second protective layer 2 / first protective layer 1 / base material are laminated in this order. A schematic cross-sectional view of an example of a three-dimensional molded film is shown. In FIG. 2, as one aspect of the laminated structure of the three-dimensional molded film of the first aspect, the adhesive layer 7 / decorative layer / primer layer / transparent resin layer / primer layer / second protective layer 2 / first protective layer A schematic cross-sectional view of an example of a three-dimensional molded film in which 1 / substrates are laminated in this order is shown.

Further, as the laminated structure of the three-dimensional molded film of the second aspect of the present invention, the laminated structure in which the second protective layer 2 / the first protective layer 1 is laminated in this order; the base material / the second protective layer 2 / Laminated structure in which the first protective layer 1 is laminated in this order; base material / decorative layer / second protective layer 2 / laminated structure in which the first protective layer 1 is laminated in this order; base material / decorative layer / A laminated structure in which the primer layer / the second protective layer 2 / the first protective layer 1 are laminated in this order; the base material / decorative layer / primer layer / transparent resin layer / primer layer / second protective layer 2 / first The protective layer 1 is laminated in this order; the base material / concealing layer / decorative layer / primer layer / transparent resin layer / primer layer / second protective layer 2 / first protective layer 1 are laminated in this order. Laminated structure; a laminated structure in which the adhesive layer 7 / base material / concealing layer / decorative layer / primer layer / transparent resin layer / primer layer / second protective layer 2 / first protective layer 1 are laminated in this order, etc. Can be mentioned. In FIG. 5, as one aspect of the laminated structure of the three-dimensional molded film of the second aspect, the substrate / decorative layer / primer layer / second protective layer 2 / first protective layer 1 are laminated in this order. A schematic cross-sectional view of an example of the original molded film is shown. In FIG. 6, as one aspect of the laminated structure of the three-dimensional molded film of the second aspect, the base material / decorative layer / primer layer / transparent resin layer / primer layer / second protective layer 2 / first protective layer 1 is shown. A schematic cross-sectional view of an example of a three-dimensional molded film laminated in this order is shown.

Composition of each layer forming a three-dimensional molded film [Base material 3]
The base material 3 is formed of a resin sheet (resin film) that serves as a support in the three-dimensional molded film of the present invention.

In the three-dimensional molded film of the first aspect, the base material 3 (transfer base material 3a) is a layer provided for transferring the transfer layer 10 to the molding resin layer 8, and also serves as a support. It is formed of a sheet (resin film). Further, the base material 3 (transfer base material 3a) can be peeled off from the first protective layer 1.

The resin component used for the transfer substrate 3a is not particularly limited and may be appropriately selected depending on the releasability from the first protective layer 1 and the like, but a thermoplastic resin is preferable. Specifically, as the thermoplastic resin, the same one as exemplified in the laminating base material 3b of the second aspect described later can be exemplified. Among these, polyethylene terephthalate (PET) resin is preferable as the transfer base material 3a. As the resin component forming the transfer substrate 3a, only one type may be used, or two or more types may be mixed and used. Further, the transfer base material 3a may be formed of a single-layer sheet of these resins, or may be formed of a multi-layer sheet of the same or different resins.

The transfer base material 3a may have an uneven shape on at least one surface, if necessary, for the purpose of imparting an uneven shape to the surface of the first protective layer 1 described later. By directly laminating the first protective layer 1 on the surface having the uneven shape of the transfer base material 3a, the uneven shape corresponding to the uneven shape of the transfer base material 3a is formed on the surface of the first protective layer 1. Can be formed. For example, by laminating the first protective layer 1 directly on the transfer base material 3a having a fine uneven shape on the surface, the uneven shape is transferred to the surface of the first protective layer 1 and the first protection is performed. A matte design can be imparted to the surface of the layer 1. A surface having such a fine uneven shape is generally more easily scratched than a smooth surface that can receive a load because the uneven shape is destroyed by receiving a load at a point. However, as will be described later, in the transfer film of the present invention, the first protective layer 1 is formed of a cured product of an ionizing radiation curable resin composition containing a caprolactone-based urethane (meth) acrylate. Therefore, the scratch resistance of the surface is enhanced. Therefore, in the present invention, excellent scratch resistance is exhibited even for the first protective layer 1 having a matte design based on a fine uneven shape.

As a method for forming an uneven shape on the surface of the transfer substrate 3a, there are physical methods such as sandblasting, hairline processing, laser processing, embossing, and chemical methods such as corrosion treatment with chemicals or solvents. An example is a method in which the shape of the fine particles is exposed on the surface of the transfer base material 3a by containing the fine particles in the transfer base material 3a. Among these, in order to transfer a fine uneven shape to the first protective layer 1 to express a matte design, a method of containing fine particles in the transfer base material 3a is preferably used.

Typical examples of the fine particles include synthetic resin particles and inorganic particles, but it is particularly preferable to use synthetic resin particles from the viewpoint of improving three-dimensional moldability. The synthetic resin particles are not particularly limited as long as they are particles formed of synthetic resin, and are, for example, acrylic beads, urethane beads, silicone beads, nylon beads, styrene beads, melamine beads, urethane acrylic beads, polyester beads, and polyethylene. Beads and the like can be mentioned. Among these synthetic resin particles, acrylic beads, urethane beads, and silicone beads are preferable from the viewpoint of forming an uneven shape having excellent scratch resistance on the first protective layer 1. Examples of the inorganic particles include calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, lithium phosphate, magnesium phosphate, calcium phosphate, aluminum oxide, silicon oxide, kaolin and the like. These fine particles may be used alone or in combination of two or more. The particle size of the fine particles is preferably about 0.3 to 25 μm, more preferably about 0.5 to 5 μm. The particle size of the fine particles in the present invention is dispersed in the air by injecting the powder to be measured from the nozzle using compressed air using the Shimadzu laser diffraction type particle size distribution measuring device SALD-2100-WJA1. It refers to the one by the jet type dry measurement method to measure by letting.

The content of the fine particles contained in the transfer base material 3a is not particularly limited as long as a desired uneven shape is formed on the first protective layer 1, and for example, 100 parts by mass of the resin contained in the transfer base material 3a. On the other hand, preferably about 1 to 100 parts by mass, more preferably about 5 to 80 parts by mass. Further, various stabilizers, lubricants, antioxidants, antistatic agents, antifoaming agents, fluorescent whitening agents and the like can be added to the transfer substrate 3a, if necessary.

The polyester sheet suitably used as the transfer base material 3a in the present invention is produced, for example, as follows. First, the above polyester resin and other raw materials are supplied to a well-known melt extruder such as an extruder, and heated to a temperature equal to or higher than the melting point of the polyester resin to melt. Then, while extruding the molten polymer, it is rapidly cooled and solidified on a rotary cooling drum so as to have a temperature equal to or lower than the glass transition temperature to obtain a substantially amorphous unoriented sheet. It is obtained by stretching this sheet in the biaxial direction to form a sheet and heat-fixing it. In this case, the stretching method may be sequential biaxial stretching or simultaneous biaxial stretching. Further, if necessary, it may be stretched again in the vertical and / or horizontal directions before or after heat fixing. In the present invention, in order to obtain sufficient dimensional stability, the stretch ratio is preferably 7 times or less, more preferably 5 times or less, still more preferably 3 times or less. Within this range, when the obtained polyester sheet is used for the three-dimensional molded film, the three-dimensional molded film does not shrink again in the temperature range when the molding resin is injected, and the sheet strength required in the temperature range is reached. Can be obtained. The polyester sheet may be manufactured as described above, or a commercially available polyester sheet may be used.

Further, when the release layer described later is provided, the transfer base material 3a may be physically or unevenly formed on one side or both sides, if desired, for the purpose of improving the adhesion to the release layer. Chemical surface treatment can be applied. Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method, and examples of the unevenness method include sandblasting method and solvent treatment method. These surface treatments are appropriately selected depending on the type of the transfer substrate 3a, but in general, the corona discharge treatment method is preferably used from the viewpoints of effectiveness and operability. Further, the transfer base material 3a may be subjected to a treatment such as forming an easy-adhesion layer for the purpose of enhancing the interlayer adhesion between the transfer base material 3a and the layer provided on the transfer base material 3a. When a commercially available polyester sheet is used, the commercially available product may be one that has been subjected to the above-mentioned surface treatment in advance or one that is provided with an easy-adhesive layer.

The thickness of the transfer substrate 3a is not particularly limited and is appropriately set according to the intended use of the three-dimensional molded film, but is usually about 10 to 150 μm, preferably about 10 to 125 μm, and more preferably about 10 to 80 μm. Can be mentioned.

Further, in the three-dimensional molded film of the second aspect, the resin component used for the base material 3 (base material for lamination 3b) is not particularly limited, and the three-dimensional moldability, compatibility with the molding resin layer, and the like are not particularly limited. It may be appropriately selected according to the situation, but a thermoplastic resin is preferable. Specific examples of the thermoplastic resin include acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as "ABS resin"); acrylonitrile-styrene-acrylic acid ester resin; acrylic resin; polyolefin-based resins such as polypropylene and polyethylene. Examples thereof include resin; polycarbonate resin; vinyl chloride resin; polyethylene terephthalate (PET) resin and the like. Among these, ABS resin is preferable from the viewpoint of three-dimensional moldability. As the resin component forming the laminating base material 3b, only one type may be used, or two or more types may be mixed and used. Further, the laminating base material 3b may be formed of a single-layer sheet of these resins, or may be formed of a multi-layer sheet of the same or different resins.

The laminated base material 3b may be subjected to physical or chemical surface treatment such as an oxidation method or an unevenness method on one side or both sides, if necessary, in order to improve the adhesion to the adjacent layer. good. Examples of the oxidation method performed as the surface treatment of the base material 3 include a corona discharge treatment, a plasma treatment, a chromium oxidation treatment, a flame treatment, a hot air treatment, and an ozone ultraviolet treatment method. In addition, examples of the unevenness method performed as the surface treatment of the laminating base material 3b include a sandblast method and a solvent treatment method. These surface treatments are appropriately selected depending on the type of resin component constituting the laminating base material 3b, and from the viewpoint of effectiveness and operability, a corona discharge treatment method is preferable.

Further, the laminating base material 3b may be colored by blending a colorant or the like, painted to adjust the color, or formed a pattern to impart designability.

The thickness of the laminating base material 3b is not particularly limited and is appropriately set according to the use of the three-dimensional molded film, and is, for example, about 50 to 800 μm, preferably about 100 to 600 μm, and more preferably about 200 to 500 μm. Can be mentioned. When the thickness of the laminating base material 3b is within the above range, it is possible to provide the three-dimensional molded film with even better three-dimensional moldability and the like.

[Release layer]
The release layer is provided between the transfer base material 3a and the first protective layer 1 as needed in the three-dimensional molded film of the first aspect. The release layer is a layer having a role of enhancing the peelability of the transfer base material 3a from the first protective layer 1.

The release layer may be a solid release layer that covers the entire surface of the transfer substrate 3a (the entire surface is solid), or may be provided on a part of the release layer. Usually, a solid release layer is preferable in consideration of peelability.

The release layer includes a silicone resin, a fluororesin, an acrylic resin (for example, an acrylic-melamine resin is included), a polyester resin, a polyolefin resin, a polystyrene resin, a polyurethane resin, and a cellulose resin. Vinyl chloride-vinyl acetate copolymer resin, thermoplastic resin such as vitrified cotton, copolymer of the monomer forming the thermoplastic resin, ionizing radiation curable resin, or these resins are (meth) acrylic acid or urethane. The one modified with the above can be formed by using a resin composition alone or a mixture of a plurality of the same. Among them, acrylic resins, polyester resins, polyolefin resins, polystyrene resins, copolymers of monomers forming these resins, and urethane-modified products thereof are preferable, and more specifically, acrylic-melamine. A resin composition alone, an acrylic-melamine resin-containing composition, a resin composition obtained by mixing a polyester resin with a urethane-modified copolymer of ethylene and acrylic acid, and a copolymer of an acrylic resin and styrene and acrylic. Examples thereof include a resin composition mixed with the above emulsion. Of these, it is particularly preferable to form the release layer with an acrylic-melamine resin alone or a composition containing 50% by mass or more of the acrylic-melamine resin.

The release layer may have an uneven shape on the surface on the side of the first protective layer 1 for the purpose of imparting an uneven shape to the surface of the first protective layer 1 described later. By directly laminating the first protective layer 1 on the surface having the uneven shape of the release layer, it is possible to form an uneven shape corresponding to the uneven shape of the release layer on the surface of the first protective layer 1. can. For example, by laminating the first protective layer 1 directly on the release layer having a fine uneven shape on the surface, the uneven shape is transferred to the surface of the first protective layer 1, and the first protective layer 1 is transferred. A matte design can be given to the surface of the mold. As described above for the transfer substrate 3a, a surface having a fine uneven shape that expresses a matte design generally has a problem that it is easily scratched, but in the present invention, the fine uneven shape is present. The first protective layer 1 having a matte design based on the above also exhibits excellent scratch resistance.

As a method for forming an uneven shape on the surface of the release layer, the same method as the above-mentioned transfer substrate 3a can be exemplified. Among these methods, a method of incorporating fine particles in the release layer is preferable from the viewpoint of transferring a fine uneven shape to the first protective layer 1 to express a matte design, and a viewpoint of improving three-dimensional moldability. A method of incorporating synthetic resin particles from the above is particularly preferable.

The content of the fine particles contained in the release layer is not particularly limited as long as a desired uneven shape is formed on the first protective layer 1, and for example, with respect to 100 parts by mass of the resin contained in the release layer. About 1 to 100 parts by mass, preferably about 5 to 80 parts by mass may be mentioned.

When the release layer contains fine particles, it is preferable that the release layer is formed of a cured product of a resin composition containing the fine particles and an ionizing radiation curable resin. In the three-dimensional molded film of the present invention, the release layer is formed of such a cured product, and the first protective layer 1 is an ionizing radiation curable resin composition containing a caprolactone-based urethane (meth) acrylate. Since it is formed of a cured product of an object, fine uneven shapes due to fine particles are suitably transferred to the surface of the first protective layer 1, and the surface of the first protective layer 1 is a mat with excellent scratch resistance. A design can be given. Hereinafter, the ionizing radiation curable resin used for forming the release layer will be described in detail.

(Ionizing radiation curable resin)
The ionizing radiation curable resin used for forming the release layer is a resin that is crosslinked and cured by irradiation with ionizing radiation, and specifically, a polymerizable unsaturated bond or an epoxy group is formed in the molecule. Examples thereof include those obtained by appropriately mixing at least one of the prepolymers, oligomers, monomers and the like. Here, the ionizing radiation is as described in the column of [1st protective layer 1] described later.

As the above-mentioned monomer used as the ionizing radiation curable resin, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth) acrylate monomer is particularly preferable. The polyfunctional (meth) acrylate monomer may be a (meth) acrylate monomer having two or more (bifunctional or higher), preferably three or more (trifunctional or higher) polymerizable unsaturated bonds in the molecule. Specific examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di (). Meta) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyldi (meth) acrylate, caprolactone-modified dicyclopentenyldi (meth) Meta) acrylate, ethylene oxide-modified di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylol propanetri (meth) acrylate, ethylene oxide-modified trimethylol propanetri (meth) acrylate , Dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylol propanetri (meth) acrylate, tris (acryloxyethyl) isocyanurate , Propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate and the like. These monomers may be used alone or in combination of two or more.

Further, as the above-mentioned oligomer used as an ionizing radiation curable resin, a (meth) acrylate oligomer having a radically polymerizable unsaturated group in the molecule is suitable, and among them, two or more polymerizable unsaturated bonds in the molecule. A polyfunctional (meth) acrylate oligomer having (bifunctional or higher) is preferable. Examples of the polyfunctional (meth) acrylate oligomer include polycarbonate (meth) acrylate, acrylic silicone (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate. , Polybutadiene (meth) acrylate, silicone (meth) acrylate, oligomers having a cationically polymerizable functional group in the molecule (for example, novolak type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.) and the like. .. Here, the polycarbonate (meth) acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and has a (meth) acrylate group in the terminal or side chain, and for example, a polycarbonate polyol (meth) is used. It can be obtained by esterifying with acrylic acid. The polycarbonate (meth) acrylate may be, for example, urethane (meth) acrylate having a polycarbonate skeleton. Urethane (meth) acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol with a polyhydric isocyanate compound and a hydroxy (meth) acrylate. Acrylic silicone (meth) acrylate can be obtained by radically copolymerizing a silicone macromonomer with a (meth) acrylate monomer. Urethane (meth) acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reacting a polyether polyol, a polyester polyol, or a caprolactone-based polyol with a polyisocyanate compound with (meth) acrylic acid. Epoxy (meth) acrylate can be obtained, for example, by reacting (meth) acrylic acid with an oxylan ring of a relatively low molecular weight bisphenol type epoxy resin or a novolak type epoxy resin to esterify it. Further, a carboxyl-modified epoxy (meth) acrylate obtained by partially modifying this epoxy (meth) acrylate with a dibasic carboxylic acid anhydride can also be used. The polyester (meth) acrylate can be obtained, for example, by esterifying the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, or to a polyvalent carboxylic acid. It can be obtained by esterifying the hydroxyl group at the end of the oligomer obtained by adding an alkylene oxide with (meth) acrylic acid. The polyether (meth) acrylate can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid. Polybutadiene (meth) acrylate can be obtained by adding (meth) acrylic acid to the side chain of the polybutadiene oligomer. The silicone (meth) acrylate can be obtained by adding (meth) acrylic acid to the terminal or side chain of a silicone having a polysiloxane bond in the main chain. Among these, as the polyfunctional (meth) acrylate oligomer, polycarbonate (meth) acrylate, urethane (meth) acrylate and the like are particularly preferable. These oligomers may be used alone or in combination of two or more.

Among the above-mentioned ionizing radiation curable resins, a matte design having excellent scratch resistance is appropriately transferred to the surface of the first protective layer 1 with fine uneven shapes due to fine particles, and the surface of the first protective layer 1 is provided with a matte design. From the viewpoint of imparting, it is preferable to use at least one of polycarbonate (meth) acrylate and urethane (meth) acrylate.

When forming a release layer using an ionizing radiation curable resin, for forming the release layer, for example, an ionizing radiation curable resin composition containing fine particles and an ionizing radiation curable resin is prepared and coated. It is performed by cross-linking and curing. The viscosity of the ionizing radiation curable resin composition may be any viscosity that can form an uncured resin layer by the coating method described later.

In the present invention, the prepared coating liquid is applied by a known method such as gravure coat, bar coat, roll coat, reverse roll coat, comma coat, preferably gravure coat so as to have the above-mentioned thickness, and is uncured. Form a resin layer.

The uncured resin layer thus formed is irradiated with ionizing radiation such as an electron beam and ultraviolet rays to cure the uncured resin layer to form a release layer. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage thereof can be appropriately selected depending on the resin to be used and the thickness of the layer, but usually an acceleration voltage of about 70 to 300 kV can be mentioned.

In electron beam irradiation, the higher the acceleration voltage, the higher the transmission capacity. Therefore, when a resin that is easily deteriorated by electron beam irradiation is used under the release layer, the electron beam transmission depth and the release layer are used. The acceleration voltage is selected so that the thicknesses of the are substantially equal. As a result, it is possible to suppress the irradiation of the layer located below the release layer with the extra electron beam, and it is possible to minimize the deterioration of each layer due to the excess electron beam.

The irradiation dose is preferably an amount at which the crosslink density of the release layer is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).

Further, the electron beam source is not particularly limited, and various electron beam accelerators such as a cockloft Walton type, a van de Graaff type, a resonance transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. Can be used.

When ultraviolet rays are used as ionizing radiation, light rays including ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. The ultraviolet source is not particularly limited, and examples thereof include a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, and an ultraviolet light emitting diode (LED-UV).

The thickness of the release layer is usually about 0.01 to 5 μm, preferably about 0.05 to 3 μm.

[First protective layer 1]
The first protective layer 1 is a layer provided on the three-dimensional molded film so as to be located on the outermost surface of the resin molded product for the purpose of enhancing the scratch resistance, weather resistance, chemical resistance, etc. of the resin molded product. Is.

One of the features of the present invention is that the first protective layer 1 is formed of a cured product of an ionized radiation curable resin composition containing a caprolactone-based urethane (meth) acrylate, which will be further described later. Since the second protective layer 2 is formed of a cured product of an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate, a three-dimensional molded film having both excellent scratch resistance and excellent durability is provided. Become.

<Ionizing radiation curable resin>
The ionizing radiation curable resin is a resin that is crosslinked and cured by irradiation with ionizing radiation, and specifically, a prepolymer, an oligomer, and a monomer having a polymerizable unsaturated bond or an epoxy group in the molecule. Examples thereof include those obtained by appropriately mixing at least one of these. Here, ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually ultraviolet (UV) or electron beam (EB) is used, but in addition, X It also includes electromagnetic waves such as rays and γ rays, and charged particle beams such as α rays and ion rays. Among the ionizing radiation curable resins, the electron beam curable resin can be made solvent-free, does not require a photopolymerization initiator, and stable curing characteristics can be obtained. Therefore, the first protective layer 1 is formed. Suitable for use in.

<Caprolactone urethane (meth) acrylate>
The caprolactone-based urethane (meth) acrylate used for the first protective layer 1 is a resin having ionizing radiation curability, and can be usually obtained by reacting a caprolactone-based polyol with an organic polyisocyanate and a hydroxy (meth) acrylate. It is a thing.

Examples of the caprolactone-based polyol include those having two hydroxyl groups, preferably having a weight average molecular weight of 500 to 3000, and more preferably 750 to 2000. Further, polyols other than caprolactone-based polyols, for example, polyols such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol can be used by mixing one or more in any ratio.

As the organic polyisocyanate, a diisocyanate having two isocyanate groups is preferable, and from the viewpoint of suppressing yellowing, isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, trimethylhexamethylene diisocyanate and the like are preferably mentioned. .. Further, as the hydroxy (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, caprolactone-modified -2-hydroxyethyl (meth) acrylate and the like are preferably mentioned.

Caprolactone-based urethane (meth) acrylates can be synthesized by reacting these polycaprolactone-based polyols with organic polyisocyanates and hydroxy (meth) acrylates. As a synthetic method, a polycaprolactone-based polyol is reacted with an organic polyisocyanate to form a polyurethane prepolymer containing a -NCO group (isocyanate group) at both ends, and then reacted with a hydroxy (meth) acrylate. The method is preferred. The reaction conditions and the like may be in accordance with a conventional method. As the caprolactone-based urethane (meth) acrylate, a commercially available product can also be used.

The caprolactone-based urethane (meth) acrylate used in the present invention preferably has a weight average molecular weight (polystyrene-equivalent weight average molecular weight measured by the GPC method) of 1000 to 12000, more preferably 1000 to 10000. That is, the caprolactone-based urethane (meth) acrylate is preferably an oligomer. When the weight average molecular weight is within the above range (oligomer), the processability is excellent and the coating agent composition can obtain appropriate thixotropic properties, so that the first protective layer 1 can be easily formed.

The content of the caprolactone-based urethane (meth) acrylate in the ionizing radiation curable resin composition forming the first protective layer 1 is not particularly limited, but from the viewpoint of further improving the scratch resistance and durability, the content is not particularly limited. It is preferably about 98 to 50% by mass, and more preferably about 95 to 60% by mass.

In the present invention, it is preferable that the ionizing radiation curable resin composition forming the first protective layer 1 further contains an isocyanate compound in addition to the caprolactone-based urethane (meth) acrylate.

<Isocyanate compound>
The isocyanate compound is not particularly limited as long as it is a compound having an isocyanate group, but a polyfunctional isocyanate compound having two or more isocyanate groups is preferable. Examples of the polyfunctional isocyanate include aromatic isocyanates such as 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), naphthalenedi isocyanate, and 4,4-diphenylmethane diisocyanate, or 1,6-hexamethylene diisocyanate (1,6-hexamethylene diisocyanate). Examples thereof include polyisocyanates such as aliphatic (or alicyclic) isocyanates such as HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. In addition, adducts or multimers of these various isocyanates, such as adducts of tolylene diisocyanate, trimers of tolylene diisocyanate, blocked isocyanate compounds, and the like can also be mentioned. One type of isocyanate compound may be used alone, or two or more types may be used in combination.

The content of the isocyanate compound in the ionizing radiation curable resin composition forming the first protective layer 1 is not particularly limited, but is preferably ionizing radiation curing from the viewpoint of further improving scratch resistance and durability. About 1 to 10 parts by mass, more preferably about 3 to 7 parts by mass with respect to 100 parts by mass of the solid content other than the isocyanate compound in the sex resin composition.

<Other additive ingredients>
The ionizing thermosetting resin composition forming the first protective layer 1 may include an ionizing thermosetting resin other than the caprolactone-based urethane (meth) acrylate, depending on the desired physical properties to be provided in the first protective layer 1. , Thermoplastic resin, thermosetting resin, and various additives can be blended. Examples of this additive include weather resistance improvers such as ultraviolet absorbers and light stabilizers, wear resistance improvers, polymerization inhibitors, cross-linking agents, infrared absorbers, antistatic agents, adhesiveness improvers, and leveling agents. Examples thereof include a thixophilic imparting agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, a coloring agent, a matting agent and the like. These additives can be appropriately selected from commonly used additives, and examples of the matting agent include silica particles and aluminum hydroxide particles. Further, as the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can also be used.

The first protective layer 1 preferably contains at least one of an ultraviolet absorber and a light stabilizer, and more preferably contains an ultraviolet absorber and a light stabilizer.

<UV absorber>
As the ultraviolet absorber, for example, the following (1) to (5) can be preferably used.
(1) Benzophenone system: 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid, etc. ,
(2) Benzotriazole system: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzo Triazole, 2- (2'-hydroxy-3', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-dicumylphenyl) phenylbenzo Triazole, 2- (2'-hydroxy-3'-dodecyl-5'-methylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- ( 2H-benzotriazole-2-yl) phenol], etc.
(3) Acrylate system: ethyl-2-cyano-3,3'-diphenylacrylate, 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, etc.
(4) Salicylate system: Phenyl salicylate, 4-t-butylphenyl salicylate, etc.
(5) Oxanilide system: 2-ethoxy-2'-ethyloxalic acidobisanilide, 2-ethoxyquin-5-t-butyl-2'-ethyloxalic acidobisanilide, etc.
(6) Triazine system: 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-[(hexyl) oxy] phenol, 1,3,5-triazine-2,4 6 (1H, 3H, 5H) -trione, 1,3,5-tri [[3,5-bis- (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] and the like.

Among these, (6) triazine-based ultraviolet absorber is preferable. The ultraviolet absorber may be used alone or in combination of two or more.

<Light stabilizer>
Examples of the light stabilizer include hindered amines, specifically 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2'-n-butylmalonate bis (1,2,2,6). , 6-Pentamethyl-4-piperidyl), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sevacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1, Examples thereof include 2,3,4-butanetetracarboxylate.

The content of the ultraviolet absorber contained in the first protective layer 1 is preferably a solid content other than the ultraviolet absorber in the ionizing radiation curable resin composition from the viewpoint of further improving scratch resistance and durability. About 0.5 to 10 parts by mass, more preferably about 1 to 5 parts by mass with respect to 100 parts by mass. Further, the content of the light stabilizer contained in the first protective layer 1 is preferably other than the light stabilizer in the ionizing radiation curable resin composition from the viewpoint of further improving the scratch resistance and durability. About 0.5 to 10 parts by mass, more preferably about 1 to 5 parts by mass with respect to 100 parts by mass of solid content.

<Thickness of the first protective layer 1>
The thickness of the first protective layer 1 after curing is not particularly limited, and examples thereof include about 1 to 10 μm, preferably about 2 to 8 μm, and more preferably about 4 to 8 μm. When the thickness in such a range is satisfied, sufficient physical properties as a protective layer can be obtained from the viewpoint of scratch resistance, weather resistance, etc., and ionizing radiation can be uniformly irradiated, so that the material is uniformly cured. Is possible, which is economically advantageous. Further, when the thickness of the first protective layer 1 after curing satisfies the above range, the three-dimensional moldability of the three-dimensional molded film is further improved, which is high for complicated three-dimensional shapes such as automobile interior applications. Followability can be obtained. As described above, in the three-dimensional molded film of the present invention, even if the thickness of the first protective layer 1 is made thicker than that of the conventional one, sufficiently high three-dimensional moldability can be obtained. It is also useful as a three-dimensional molded film for members that require a high film thickness, for example, vehicle exterior parts.

<Formation of the first protective layer 1>
The formation of the first protective layer 1 is performed, for example, by preparing an ionizing radiation curable resin composition containing caprolactone-based urethane (meth) acrylate, applying the same, and cross-linking and curing. The viscosity of the ionizing radiation curable resin composition is determined by a layer located below when the first protective layer is formed (for example, the second protective layer 2 (cured or uncured)) by the coating method described later. The viscosity may be such that an uncured resin layer can be formed on the surface of the transfer substrate 3a or the release layer.

In the present invention, the prepared coating liquid is applied onto the surface of the transfer substrate 3a or the release layer so as to have the above-mentioned thickness, such as a gravure coat, a bar coat, a roll coat, a reverse roll coat, and a comma coat. It is applied by a known method, preferably a gravure coat, to form an uncured resin layer.

The uncured resin layer thus formed is irradiated with ionizing radiation such as an electron beam and ultraviolet rays to cure the uncured resin layer to form the first protective layer 1. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage thereof can be appropriately selected depending on the resin to be used and the thickness of the layer, but usually an acceleration voltage of about 70 to 300 kV can be mentioned.

In electron beam irradiation, the higher the acceleration voltage, the higher the transmission capacity. Therefore, when a resin that is easily deteriorated by electron beam irradiation is used under the first protective layer 1, the transmission depth of the electron beam is increased. The acceleration voltage is selected so that the thickness of the first protective layer 1 is substantially equal. As a result, it is possible to suppress the irradiation of the layer located below the first protective layer 1 with the extra electron beam, and it is possible to minimize the deterioration of each layer due to the excess electron beam.

The irradiation dose is preferably an amount at which the crosslink density of the first protective layer 1 is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad). ..

Further, the electron beam source is not particularly limited, and various electron beam accelerators such as a cockloft Walton type, a van de Graaff type, a resonance transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. Can be used.

When ultraviolet rays are used as ionizing radiation, light rays including ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. The ultraviolet source is not particularly limited, and examples thereof include a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, and an ultraviolet light emitting diode (LED-UV).

By adding various additives to the first protective layer 1 thus formed, a hard coat function, an anti-fog coat function, an anti-fouling coat function, an anti-glare coat function, an anti-reflection coat function, and an ultraviolet shielding coat are applied. A process for imparting a function, an infrared shielding coat function, or the like may be performed.

[Second protective layer 2]
The second protective layer 2 is positioned below the first protective layer 1 in the resin molded product for the purpose of enhancing the scratch resistance, weather resistance, chemical resistance, etc. of the resin molded product. This is a layer provided on the original molded film.

One of the features of the present invention is that the second protective layer 2 is formed of a cured product of an ionized radiation curable resin composition containing a polycarbonate (meth) acrylate, and further, the above-mentioned first protective layer 2 is formed. Since the protective layer 1 is formed of a cured product of an ionized radiation curable resin composition containing a caprolactone-based urethane (meth) acrylate, a three-dimensional molded film having excellent scratch resistance and excellent durability is formed. Become.

The polycarbonate (meth) acrylate used for forming the second protective layer 2 is not particularly limited as long as it has a carbonate bond in the polymer main chain and a (meth) acrylate group in the terminal or side chain. For example, it can be obtained by esterifying a polycarbonate polyol with (meth) acrylic acid. This (meth) acrylate preferably has bifunctionality or more from the viewpoint of crosslinking and curing. The polycarbonate (meth) acrylate may be, for example, a polycarbonate-based urethane (meth) acrylate which is a urethane (meth) acrylate having a polycarbonate skeleton. Urethane (meth) acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol with a polyhydric isocyanate compound and a hydroxy (meth) acrylate.

The above-mentioned polycarbonate (meth) acrylate is obtained, for example, by converting some or all of the hydroxyl groups of the polycarbonate polyol into (meth) acrylate (acrylic acid ester or methacrylic acid ester). This esterification reaction can be carried out by a usual esterification reaction. For example, 1) a method of condensing a polycarbonate polyol and an acrylic acid halide or a methacrylate halide in the presence of a base, and 2) a method of condensing a polycarbonate polyol and an acrylic acid anhydride or a methacrylate anhydride in the presence of a catalyst. Alternatively, 3) a method of condensing a polycarbonate polyol and acrylic acid or methacrylic acid in the presence of an acid catalyst can be mentioned.

The above-mentioned polycarbonate polyol is a polymer having a carbonate bond in the polymer main chain and having two or more, preferably 2 to 50, more preferably 3 to 50 hydroxyl groups in the terminal or side chain. A typical method for producing this polycarbonate polyol is a method by polycondensation reaction with a diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) as a carbonyl component. The diol compound (A) used as a raw material is represented by ^{the general formula HO-R 1-OH.} Here, R ¹ is a divalent hydrocarbon group having 2 to 20 carbon atoms, and may contain an ether bond in the group. For example, a linear or branched alkylene group, a cyclohexylene group, or a phenylene group.

Specific examples of the diol compound include ethylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol, and 1, , 5-Pentindiol, 3-Methyl-1,5Pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis (2) -Hydroxyethoxy) benzene, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like can be mentioned. These diols may be used alone or in combination of two or more.

Examples of the trihydric or higher polyhydric alcohol (B) include alcohols such as trimethylolpropane, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, glycerin, and sorbitol. Further, alcohols having a hydroxyl group obtained by adding 1 to 5 equivalents of ethylene oxide, propylene oxide, or other alkylene oxide to the hydroxyl group of these polyhydric alcohols may be used. The polyhydric alcohol may be used alone or in combination of two or more.

The compound (C) to be a carbonyl component is a compound selected from a carbonic acid diester, phosgene, or an equivalent thereof. Specific examples thereof include carbonate diesters such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate and propylene carbonate, phosgene, and halogenated formic acid esters such as methyl chloroformate, ethyl chloroformate and phenyl chloroformate. And so on. These may be used alone or in combination of two or more.

The polycarbonate polyol is synthesized by polycondensation reaction of the above-mentioned diol compound (A), trihydric or higher polyhydric alcohol (B), and compound (C) as a carbonyl component under general conditions. .. For example, the charged molar ratio of the diol compound (A) to the polyhydric alcohol (B) is preferably in the range of 50:50 to 99: 1, and the diol compound of the compound (C) serving as a carbonyl component ( The charged molar ratio of A) to the polyhydric alcohol (B) is preferably 0.2 to 2 equivalents with respect to the hydroxyl groups of the diol compound and the polyhydric alcohol.

The equivalent number (eq. / Mol) of the hydroxyl groups present in the polycarbonate polyol after the polycondensation reaction at the above charging ratio is 3 or more, preferably 3 to 50, more preferably 3 to 3 on average in one molecule. 20. Within this range, a required amount of (meth) acrylate groups are formed by the esterification reaction described later, and appropriate flexibility is imparted to the polycarbonate (meth) acrylate resin. The terminal functional group of this polycarbonate polyol is usually an OH group, but a part thereof may be a carbonate group.

The method for producing a polycarbonate polyol described above is described in, for example, Japanese Patent Application Laid-Open No. 64-1726. Further, as described in Japanese Patent Application Laid-Open No. 3-181517, this polycarbonate polyol can also be produced by a transesterification reaction between a polycarbonate diol and a polyhydric alcohol having a valence of 3 or more.

The molecular weight of the polycarbonate (meth) acrylate used in the present invention is preferably 500 or more, more preferably 1,000 or more, and the weight average molecular weight measured by GPC analysis and converted into standard polystyrene is preferably 500 or more. , 2,000 or more is more preferable. The upper limit of the weight average molecular weight of the polycarbonate (meth) acrylate is not particularly limited, but is preferably 100,000 or less, and more preferably 50,000 or less, from the viewpoint of controlling the viscosity so as not to become too high. From the viewpoint of achieving both scratch resistance, durability, and three-dimensional moldability, it is more preferably 10,000 or more and 50,000 or less, and particularly preferably 20,000 or more and 30,000 or less.

In the ionizing radiation curable resin composition, the polycarbonate (meth) acrylate is preferably used together with the polyfunctional (meth) acrylate. That is, the ionizing radiation curable resin composition preferably further contains a polyfunctional (meth) acrylate. The mass ratio of the polycarbonate (meth) acrylate to the polyfunctional (meth) acrylate is more preferably polycarbonate (meth) acrylate: polyfunctional (meth) acrylate = 98: 2 to 50:50. When the mass ratio of the polycarbonate (meth) acrylate to the polyfunctional (meth) acrylate is smaller than 98: 2 (that is, the amount of the polycarbonate (meth) acrylate is 98% by mass or less with respect to the total amount of the two components). , Scratch resistance is further improved. On the other hand, when the mass ratio of the polycarbonate (meth) acrylate to the polyfunctional (meth) acrylate is larger than 50:50 (that is, the amount of the polycarbonate (meth) acrylate is 50% by mass or more with respect to the total amount of the two components. ), Three-dimensional formability is further improved. Preferably, the mass ratio of polycarbonate (meth) acrylate to polyfunctional (meth) acrylate is 95: 5 to 60:40.

The polyfunctional (meth) acrylate used in the present invention may be any bifunctional or higher functional (meth) acrylate, and is not particularly limited. However, from the viewpoint of curability, trifunctional or higher (meth) acrylates are preferable. Here, the bifunctional means having two ethylenically unsaturated bonds {(meth) acryloyl group} in the molecule.

The polyfunctional (meth) acrylate may be either an oligomer or a monomer, but a polyfunctional (meth) acrylate oligomer is preferable from the viewpoint of improving three-dimensional moldability.

Examples of the polyfunctional (meth) acrylate oligomer include urethane (meth) acrylate-based oligomers, epoxy (meth) acrylate-based oligomers, polyester (meth) acrylate-based oligomers, and polyether (meth) acrylate-based oligomers. Here, the urethane (meth) acrylate-based oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by a reaction between a polyether polyol or a polyester polyol and a polyisocyanate with (meth) acrylic acid. The epoxy (meth) acrylate-based oligomer can be obtained, for example, by reacting (meth) acrylic acid with the oxylan ring of a relatively low molecular weight bisphenol type epoxy resin or a novolak type epoxy resin to esterify it. Further, a carboxyl-modified epoxy (meth) acrylate oligomer obtained by partially modifying this epoxy (meth) acrylate-based oligomer with a dibasic carboxylic acid anhydride can also be used. As the polyester (meth) acrylate-based oligomer, for example, the hydroxyl group of the polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol is esterified with (meth) acrylic acid, or many. It can be obtained by esterifying the hydroxyl group at the terminal of the oligomer obtained by adding an alkylene oxide to a valent carboxylic acid with a (meth) acrylic acid. The polyether (meth) acrylate-based oligomer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.

Further, as other polyfunctional (meth) acrylate oligomers, a highly hydrophobic polybutadiene (meth) acrylate-based oligomer having a (meth) acrylate group in the side chain of the polybutadiene oligomer, and a silicone (meth) having a polysiloxane bond in the main chain. ) Acrylate-based oligomers, aminoplast resin (meth) acrylate-based oligomers obtained by modifying an aminoplast resin having many reactive groups in a small molecule, and the like.

Specific examples of the polyfunctional (meth) acrylate monomer include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-. Hexadiol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone-modified di Cyclopentenyldi (meth) acrylate, ethylene oxide-modified di (meth) acrylate, allylated cyclohexyldi (meth) acrylate, isocyanurate di (meth) acrylate, trimethyl propanthry (meth) acrylate, ethylene oxide-modified trimethyl propanthry (Meta) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylol propantri (meth) acrylate, tris (acryloxy) Ethyl) isocyanurate, propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, etc. Be done. The polyfunctional (meth) acrylate oligomer and the polyfunctional (meth) acrylate monomer described above may be used alone or in combination of two or more.

In the present invention, the monofunctional (meth) acrylate can be appropriately used together with the polyfunctional (meth) acrylate for the purpose of lowering the viscosity thereof, as long as the object of the present invention is not impaired. Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and cyclohexyl (meth) acrylate. Examples thereof include meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate. One of these monofunctional (meth) acrylates may be used alone, or two or more thereof may be used in combination.

The content of the polycarbonate (meth) acrylate in the ionizing radiation curable resin composition forming the second protective layer 2 is not particularly limited, but from the viewpoint of further improving the three-dimensional moldability and scratch resistance, the content thereof is not particularly limited. It is preferably about 98 to 50% by mass, and more preferably about 90 to 65% by mass.

From the viewpoint of further improving the scratch resistance and durability of the three-dimensional molded film, the ionizing radiation curable resin composition forming the second protective layer 2 contains an isocyanate compound in addition to the polycarbonate (meth) acrylate. It is preferable that it is contained.

<Isocyanate compound>
The isocyanate compound is not particularly limited as long as it is a compound having an isocyanate group, but a polyfunctional isocyanate compound having two or more isocyanate groups is preferable. Examples of the polyfunctional isocyanate include aromatic isocyanates such as 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), naphthalenedi isocyanate, and 4,4-diphenylmethane diisocyanate, or 1,6-hexamethylene diisocyanate (1,6-hexamethylene diisocyanate). Examples thereof include polyisocyanates such as aliphatic (or alicyclic) isocyanates such as HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. In addition, adducts or multimers of these various isocyanates, such as adducts of tolylene diisocyanate, trimers of tolylene diisocyanate, blocked isocyanate compounds, and the like can also be mentioned. One type of isocyanate compound may be used alone, or two or more types may be used in combination.

The content of the isocyanate compound in the ionizing radiation curable resin composition forming the second protective layer 2 is not particularly limited, but is preferable from the viewpoint of further improving the scratch resistance and durability of the three-dimensional molded film. Is about 1 to 10 parts by mass, more preferably about 3 to 7 parts by mass with respect to 100 parts by mass of the solid content other than the isocyanate compound in the ionizing radiation curable resin composition.

<Other additive ingredients>
Various additives can be added to the ionizing radiation curable resin composition forming the second protective layer 2 according to the desired physical properties to be provided in the second protective layer 2. Examples of this additive include weather resistance improvers such as ultraviolet absorbers and light stabilizers, wear resistance improvers, polymerization inhibitors, cross-linking agents, infrared absorbers, antistatic agents, adhesiveness improvers, and leveling agents. Examples thereof include a thixophilic imparting agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, a coloring agent, a matting agent and the like. These additives can be appropriately selected from commonly used additives, and examples of the matting agent include silica particles and aluminum hydroxide particles. Further, as the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can also be used.

The second protective layer 2 preferably contains at least one of an ultraviolet absorber and a light stabilizer, and more preferably contains an ultraviolet absorber and a light stabilizer. Specific examples of the ultraviolet absorber and the light stabilizer include the same as those exemplified in the above-mentioned first protective layer 1. The content of the ultraviolet absorber and the light stabilizer contained in the second protective layer 2 can be the same as that of the first protective layer 1 described above.

<Thickness of the second protective layer 2>
The thickness of the second protective layer 2 after curing is not particularly limited, and examples thereof include about 1 to 10 μm, preferably about 2 to 8 μm, and more preferably about 4 to 8 μm. When the thickness in such a range is satisfied, sufficient physical properties as a protective layer can be obtained from the viewpoint of scratch resistance, weather resistance, etc., and ionizing radiation can be uniformly irradiated, so that the material is uniformly cured. Is possible, which is economically advantageous. Further, when the thickness of the second protective layer 2 after curing satisfies the above range, the three-dimensional formability of the transfer film for three-dimensional molding is further improved, so that the thickness of the second protective layer 2 can be further improved for complicated three-dimensional shapes such as automobile interior applications. High followability can be obtained. As described above, in the transfer film for three-dimensional molding of the present invention, even if the thickness of the second protective layer 2 is made thicker than that of the conventional one, sufficiently high three-dimensional moldability can be obtained, so that the second protection is particularly high. It is also useful as a member for which a high film thickness is required for the layer 2, for example, as a transfer film for three-dimensional molding of vehicle exterior parts and the like.

From the viewpoint of further improving scratch resistance and weather resistance, the total thickness of the first protective layer 1 and the second protective layer 2 is preferably about 3 to 20 μm, more preferably about 5 to 15 μm, still more preferable. Is about 7 to 10 μm.

<Formation of the second protective layer 2>
The formation of the second protective layer 2 is carried out, for example, by preparing an ionizing radiation curable resin composition containing a polycarbonate (meth) acrylate and an isocyanate compound, applying the same, and cross-linking and curing. The viscosity of the ionizing radiation curable resin composition may be any viscosity as long as it can form an uncured resin layer on the surface of the transfer substrate 3a or the release layer by the coating method described later.

In the present invention, the prepared coating liquid is applied onto the surface of the transfer substrate 3a or the release layer so as to have the above-mentioned thickness, such as a gravure coat, a bar coat, a roll coat, a reverse roll coat, and a comma coat. It is applied by a known method, preferably a gravure coat, to form an uncured resin layer.

The uncured resin layer thus formed is irradiated with ionizing radiation such as an electron beam and ultraviolet rays to cure the uncured resin layer to form a second protective layer 2. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage thereof can be appropriately selected depending on the resin to be used and the thickness of the layer, but usually an acceleration voltage of about 70 to 300 kV can be mentioned.

In electron beam irradiation, the higher the acceleration voltage, the higher the transmission capacity. Therefore, when a resin that is easily deteriorated by electron beam irradiation is used under the second protective layer 2, the transmission depth of the electron beam is increased. The acceleration voltage is selected so that the thickness of the second protective layer 2 is substantially equal. As a result, it is possible to suppress the irradiation of the layer located below the second protective layer 2 with the extra electron beam, and it is possible to minimize the deterioration of each layer due to the excess electron beam. The first protective layer 1 and the second protective layer 2 may be formed by curing at the same time.

The irradiation dose is preferably an amount at which the crosslink density of the second protective layer 2 is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad). ..

Further, the electron beam source is not particularly limited, and various electron beam accelerators such as a cockloft Walton type, a van de Graaff type, a resonance transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. Can be used.

When ultraviolet rays are used as ionizing radiation, light rays including ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. The ultraviolet source is not particularly limited, and examples thereof include a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, and an ultraviolet light emitting diode (LED-UV).

By adding various additives to the second protective layer 2 thus formed, a hard coat function, an anti-fog coat function, an anti-fouling coat function, an anti-glare coat function, an anti-reflection coat function, and an ultraviolet shielding coat are applied. A process for imparting a function, an infrared shielding coat function, or the like may be performed.

[Primer layer 4]
The primer layer 4 is provided with at least the layers thereof for the purpose of improving the adhesion between the layers of the second protective layer 2, the base material 3 (base material for lamination 3b), the decorative layer 5, the transparent resin layer 6, and the like. It is a layer provided at one place as needed. The primer layer 4 can be formed by a resin composition for forming a primer layer.

The resin used in the resin composition for forming the primer layer is not particularly limited, and is, for example, a polyol and / or a cured product thereof, a urethane resin, an acrylic resin, a (meth) acrylic-urethane copolymer resin, a polyester resin, and a butyral resin. And so on. Among these resins, preferred examples include polyols and / or cured products thereof, urethane resins, acrylic resins, and (meth) acrylic-urethane copolymer resins. These resins may be used alone or in combination of two or more.

In the present invention, the primer layer 4 is preferably formed of a resin composition containing a polyol and a urethane resin. The polyol may be a compound having two or more hydroxyl groups in the molecule, and specific examples thereof include polyester polyols, polyethylene glycols, polypropylene glycols, acrylic polyols, and polyether polyols, and acrylic polyols are preferable. Can be mentioned.

When a polyol and a urethane resin are used to form the primer layer 4, the mass ratio (polyurethane: urethane resin) of these is preferably about 5: 5 to 9.5: 0.5, more preferably 7: 3. ~ 9: 1 is mentioned.

Examples of the cured product of the polyol include urethane resin. As the urethane resin, polyurethane having a polyol (polyhydric alcohol) as a main component and an isocyanate as a cross-linking agent (curing agent) can be used.

Specific examples of the isocyanate include polyvalent isocyanates having two or more isocyanate groups in the molecule; aromatic isocyanates such as 4,4-diphenylmethane diisocyanate; hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogen. Examples thereof include aliphatic (or alicyclic group) isocyanates such as added diphenylmethane diisocyanate. When isocyanate is used as a curing agent, the content of isocyanate in the resin composition for forming a primer layer is not particularly limited, but from the viewpoint of adhesion and printability when laminating the decorative layer 5 or the like described later, it is considered. 3 to 45 parts by mass is preferable with respect to 100 parts by mass of the above-mentioned polyol, and 3 to 25 parts by mass is more preferable.

Among the above urethane resins, from the viewpoint of improving adhesion after cross-linking, a combination of an acrylic polyol or a polyester polyol as a polyol and a hexamethylene diisocyanate or a 4,4-diphenylmethane diisocyanate as a cross-linking agent is preferable; more preferably. Is a combination of an acrylic polyol and a hexamethylene diisocyanate.

The acrylic resin is not particularly limited, and is, for example, a homopolymer of a (meth) acrylic acid ester, a copolymer of two or more different (meth) acrylic acid ester monomers, or a (meth) acrylic acid ester and others. Examples thereof include a copolymer with the above-mentioned monomer. More specifically, the (meth) acrylic resin includes methyl poly (meth) acrylate, ethyl poly (meth) acrylate, propyl poly (meth) acrylate, butyl poly (meth) acrylate, and (meth) acrylate. Methyl- (meth) butyl acrylate copolymer, ethyl (meth) acrylate- (meth) butyl acrylate copolymer, ethylene- (meth) methyl acrylate copolymer, styrene-methyl acrylate- (meth) acrylate Examples thereof include (meth) acrylic acid esters such as polymers.

The (meth) acrylic-urethane copolymer resin is not particularly limited, and examples thereof include an acrylic-urethane (polyester urethane) block copolymer resin. Further, as the curing agent, the above-mentioned various isocyanates are used. The ratio of acrylic to urethane in the acrylic-urethane (polyester urethane) block copolymer resin is not particularly limited, but for example, the acrylic / urethane ratio (mass ratio) is 9/1 to 1/9, preferably 8. / 2 to 2/8 can be mentioned.

The thickness of the primer layer 4 is not particularly limited, but is, for example, about 0.1 to 10 μm, preferably about 1 to 10 μm (that is, the coating amount is, for example, about 0.1 to 10 g / m ² , preferably 1 to 10 g /. m ² ) can be mentioned. By satisfying such a thickness, the primer layer 4 can effectively enhance the adhesion between the layers of the second protective layer 2, the base material 3, the decorative layer 5, the transparent resin layer 6, and the like.

Various additives can be added to the composition forming the primer layer 4 according to the desired physical characteristics to be provided. Examples of this additive include weather resistance improvers such as ultraviolet absorbers and light stabilizers, wear resistance improvers, polymerization inhibitors, cross-linking agents, infrared absorbers, antistatic agents, adhesiveness improvers, and leveling agents. Examples thereof include a thixophilic imparting agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, a coloring agent, a matting agent and the like. These additives can be appropriately selected from commonly used additives, and examples of the matting agent include silica particles and aluminum hydroxide particles. Further, as the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can also be used.

The primer layer 4 is a gravure coat, a gravure reverse coat, a gravure offset coat, a spinner coat, a roll coat, a reverse roll coat, a kiss coat, a wheeler coat, a dip coat, and a solid coat with a silk screen, using a resin composition for forming a primer layer. It is formed by a usual coating method such as wire bar coat, flow coat, comma coat, flow coat, brush coat, spray coat, or transfer coating method. Here, the transfer coating method is a method in which a coating film of a primer layer or an adhesive layer is formed on a thin sheet (film base material), and then the surface of the target layer in the three-dimensional molded film is coated.

When the primer layer 4 is formed on the surface of the second protective layer 2, it may be formed on the second protective layer 2 after curing. Further, after forming the primer layer 4 by laminating a layer made of the composition for forming a primer layer on the layer of the ionizing radiation curable resin composition forming the second protective layer 2, the ionizing radiation curable resin is used. The layer may be irradiated with ionizing radiation and the layer made of the ionizing radiation curable resin may be cured to form the second protective layer 2.

[Decorative layer 5]
The decorative layer 5 is a layer provided as needed to impart decorativeness to the resin molded product. The decorative layer 5 is composed of, for example, a pattern layer and / or a concealing layer, a metal thin film layer, and the like. Here, the pattern layer is a layer provided for expressing a pattern such as a pattern or characters, and the concealing layer is usually a solid layer on the entire surface and is provided for concealing coloring or the like of a molding resin or the like. It is a layer. The concealing layer may be provided inside the pattern layer in order to enhance the pattern of the pattern layer, or the decorative layer 5 may be formed by the concealing layer alone. As for the metal thin film layer, the decorative layer 5 may be formed independently.

The pattern of the pattern layer is not particularly limited, and examples thereof include a pattern consisting of wood grain, stone grain, cloth grain, sand grain, geometric pattern, characters, and the like.

The pattern layer is formed by using a printing ink containing a colorant, a binder resin, and a solvent or a dispersion medium.

The colorant of the printing ink used for forming the pattern layer is not particularly limited, and is, for example, a metal such as aluminum, chromium, nickel, tin, titanium, iron phosphate, copper, gold, silver, brass, or an alloy. Metallic pigment consisting of scaly foil powder of metal compound; mica-like iron oxide, titanium dioxide-coated mica, titanium dioxide-coated bismuth oxychloride, bismuth oxychloride, titanium dioxide-coated talc, fish scale foil, colored titanium dioxide-coated mica, basic carbon dioxide Pearl luster pigments made of foil powder such as lead; fluorescent pigments such as strontium aluminate, calcium aluminate, barium aluminate, zinc sulfide, calcium sulfide; white inorganic pigments such as titanium dioxide, zinc flower, antimony trioxide, etc. Inorganic pigments such as zinc flower, petal pattern, vermilion, ultramarine, cobalt blue, titanium yellow, yellow lead, carbon black; isoindolinone yellow, Hansa yellow A, quinacridon red, permanent red 4R, phthalocyanine blue, induthren blue RS , Organic pigments such as aniline black (including dyes) and the like. These colorants may be used alone or in combination of two or more.

The binder resin for the printing ink used for forming the pattern layer is not particularly limited, but for example, acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-acetic acid. Examples thereof include vinyl copolymer resin, polyvinyl butyral resin, alkyd resin, petroleum resin, ketone resin, epoxy resin, melamine resin, fluororesin, silicone resin, fibrous derivative, rubber resin and the like. These binder resins may be used alone or in combination of two or more.

The solvent or dispersion medium of the printing ink used for forming the pattern layer is not particularly limited, and is, for example, a petroleum-based organic solvent such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; acetic acid. Ester-based organic solvents such as ethyl, butyl acetate, -2-methoxyethyl acetate, -2-ethoxyethyl acetate; alcohol-based solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol and propylene glycol. Organic solvent; Ketone-based organic solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; Ether-based organic solvent such as diethyl ether, dioxane, tetrahydrofuran; Chlorine-based organic solvent such as dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene; water, etc. Can be mentioned. These solvents or dispersion media may be used alone or in combination of two or more.

In addition, the printing ink used to form the pattern layer contains, if necessary, an antioxidant, a curing catalyst, an ultraviolet absorber, an antioxidant, a leveling agent, a thickener, an antifoaming agent, a lubricant, and the like. It may be.

The decorative layer 5 can be formed on an adjacent layer such as on the second protective layer 2 or the primer layer 4 by a known printing method such as gravure printing, flexographic printing, silk screen printing, and offset printing. When the decorative layer 5 is a combination of the pattern layer and the concealing layer, one layer may be laminated and dried, and then the other layer may be laminated and dried.

The thickness of the decorative layer 5 is not particularly limited, but may be, for example, about 1 to 40 μm, preferably about 3 to 30 μm.

The decorative layer 5 may be a metal thin film layer. Examples of the metal forming the metal thin film layer include tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, zinc, and alloys containing at least one of them. The method for forming the metal thin film layer is not particularly limited, and examples thereof include a vapor deposition method such as a vacuum vapor deposition method, a sputtering method, and an ion plating method using the above-mentioned metal. Further, in order to improve the adhesion with the adjacent layer, a primer layer using a known resin may be provided on the front surface or the back surface of the metal thin film layer.

[Transparent resin layer 6]
In the three-dimensional molded film of the present invention, the transparent resin layer 6 is a base material 3 and a second protective layer 2 as shown in FIGS. 2 and 3 for the purpose of improving the moldability of the three-dimensional molded film. In the case of the transfer type three-dimensional molded film shown in FIGS. 5 and 6, it can be provided on the opposite side of the second protective layer 2 from the base material 3. The transparent resin layer 6 is not particularly limited as long as it is transparent, and includes colorless transparent, colored transparent, translucent and the like. Examples of the resin component forming the transparent resin layer 6 include the binder resin exemplified in the decorative layer 5.

The transparent resin layer 6 contains a filler, a matting agent, a foaming agent, a flame retardant, a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a radical scavenger, and a soft component, if necessary. Various additives such as (for example, rubber) may be contained.

The transparent resin layer 6 can be formed by a known printing method such as gravure printing, flexographic printing, silk screen printing, and offset printing.

The thickness of the transparent resin layer 6 is not particularly limited, but is generally about 0.1 to 10 μm, preferably about 1 to 10 μm.

[Adhesive layer 7]
The adhesive layer 7 is a layer provided on the outermost surface of the three-dimensional molded film on the molding resin layer side, if necessary, for the purpose of improving the adhesiveness and adhesion between the three-dimensional molded film and the molding resin. .. The resin forming the adhesive layer 7 is not particularly limited as long as it can improve the adhesiveness and adhesion between the three-dimensional molded film and the molded resin, and is, for example, a thermoplastic resin or a thermosetting resin. Is used. Examples of the thermoplastic resin include acrylic resin, acrylic modified polyolefin resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer, thermoplastic urethane resin, thermoplastic polyester resin, polyamide resin, rubber resin and the like. .. One type of thermoplastic resin may be used alone, or two or more types may be used in combination. Examples of the thermosetting resin include urethane resin and epoxy resin. One type of thermosetting resin may be used alone, or two or more types may be used in combination.

In the three-dimensional molded film of the present invention, the adhesive layer 7 can be provided for the purpose of improving the adhesion to the molded resin layer 8, and for example, the three-dimensional molded film of the first aspect is decorated. It is preferable to provide it under the layer or the like (that is, the side to be laminated with the molding resin layer 8).

2. 2. Resin molded product and its manufacturing method The resin molded product of the present invention is formed by integrating a molding resin into the three-dimensional molding film of the present invention. That is, the resin molded product of the present invention includes at least a molded resin layer, a second protective layer 2, and a first protective layer 1 in this order, and the first protective layer 1 is a caprolactone-based urethane (meth). ) The second protective layer 2 is formed of a cured product of an ionizing radiation curable resin composition containing an acrylate, and the second protective layer 2 is formed of a cured product of an ionizing radiation curable resin composition containing a polycarbonate (meth) acrylate. It is characterized by that. In the resin molded product of the present invention, if necessary, the above-mentioned base material 3 (lamination base material 3b), primer layer 4, decorative layer 5, transparent resin layer 6, concealing layer, adhesive layer, etc. are added to the three-dimensional molded film. At least one layer of the above may be further provided.

In the above-mentioned first aspect, as shown in FIG. 3, the transfer base material 3a may be provided on the resin molded product (the resin molded product in such a state is also referred to as the resin molded product with the transfer base material). Say). FIG. 4 is a resin molded product obtained by peeling a transfer base material from the resin molded product with a transfer base material shown in FIG. 3, and the molded resin layer 8 is laminated on the three-dimensional molded film shown in FIG. It has a configured configuration. Further, in the above-mentioned second aspect as shown in FIGS. 5 and 6, the base material 3 may be provided on the resin molded product. FIG. 7 is a cross-sectional view of a resin molded product in which the molding resin layer 8 is laminated on the three-dimensional molding film shown in FIG.

The resin molded product of the present invention is produced by various injection molding methods such as an insert molding method, an injection molding simultaneous decoration method, a blow molding method, and a gas injection molding method, using the three-dimensional molding film of the present invention. .. Among these injection molding methods, an insert molding method and an injection molding simultaneous decoration method are preferably mentioned.

In the insert molding method, first, in the vacuum forming step, the three-dimensional molded film of the present invention is vacuum-formed (offline pre-molding) into the surface shape of the molded product in advance by a vacuum forming mold, and then the excess portion is trimmed if necessary. To obtain a molded sheet. This molding sheet is inserted into an injection molding mold, the injection molding mold is molded, the fluid resin is injected into the mold and solidified, and at the same time as the injection molding, a three-dimensional molding film is applied to the outer surface of the resin molded product. By integrating, a resin molded product is manufactured.

More specifically, the resin molded product of the present invention is manufactured by an insert molding method including the following steps.
A vacuum molding step of preliminarily molding the three-dimensional molded film of the present invention into a three-dimensional shape by a vacuum molding die, a trimming step of trimming an excess portion of the vacuum-molded three-dimensional molded film to obtain a molded sheet, and injection of a molded sheet. An integration process that inserts into a molding mold, closes the injection molding mold, injects a fluid resin into the injection molding mold, and integrates the resin and the molding sheet.

In the vacuum forming step in the insert forming method, the three-dimensional forming film may be heated and formed. The heating temperature at this time is not particularly limited and may be appropriately selected depending on the type of resin constituting the three-dimensional molded film, the thickness of the three-dimensional molded film, and the like. For example, when an ABS resin film is used as the base material. If this is the case, the temperature can usually be about 120 to 200 ° C. Further, in the integration step, the temperature of the resin in the flowing state is not particularly limited, but can usually be about 180 to 320 ° C.

Further, in the injection molding simultaneous decoration method, the three-dimensional molding film of the present invention is placed in a female mold that also serves as a vacuum molding mold provided with a suction hole for injection molding, and pre-molding (in-line pre-molding) is performed with this female mold. After that, the injection molding mold is molded, the fluid resin is injection-filled in the mold and solidified, and at the same time as the injection molding, the three-dimensional molding film of the present invention is integrated on the outer surface of the resin molded product. By making it a resin molded product, a resin molded product is manufactured.

More specifically, the resin molded product of the present invention is produced by an injection molding simultaneous decoration method including the following steps.
After installing the three-dimensional molded film of the present invention so that the surface of the base material of the three-dimensional molded film faces the molding surface of the movable mold having a molding surface having a predetermined shape, the three-dimensional molding film is placed. Pre-molding step of pre-molding a three-dimensional molded film by heating and softening and vacuum suctioning from the movable mold side to bring the softened three-dimensional molded film into close contact with the molding surface of the movable mold.
After molding a movable mold having a three-dimensional molded film adhered along the molding surface and a fixed mold, a fluid resin is injected and filled into the cavity formed by both molds to solidify. The resin molded body is formed by forming a resin molded body, and the integrated step of laminating and integrating the resin molded body and the three-dimensional molded film, and the movable mold is separated from the fixed mold, and all the layers of the three-dimensional molded film are laminated. The taking-out process of taking out the resin molded product.

In the preforming process of the injection molding simultaneous decoration method, the heating temperature of the three-dimensional molded film is not particularly limited, and may be appropriately selected depending on the type of resin constituting the three-dimensional molded film, the thickness of the three-dimensional molded film, and the like. However, when a polyester resin film or an acrylic resin film is used as the base material, the temperature can usually be about 70 to 130 ° C. Further, in the injection molding step, the temperature of the resin in the fluid state is not particularly limited, but can usually be about 180 to 320 ° C.

Further, the resin molded product of the present invention can also be subjected to a decoration method such as a vacuum crimping method in which the three-dimensional molded film of the present invention is attached onto a three-dimensional resin molded body (molding resin layer) prepared in advance. Can be made.

In the vacuum crimping method, first, the three-dimensional molded film and the resin molded body of the present invention are placed in a vacuum crimping machine consisting of a first vacuum chamber located on the upper side and a second vacuum chamber located on the lower side. Installed in the vacuum crimping machine so that the first vacuum chamber side and the resin molded body are on the second vacuum chamber side and the base material side of the three-dimensional molded film faces the resin molded body side, and the two vacuum chambers are in a vacuum state. And. The resin molded body is installed on an elevating table that can be raised and lowered up and down, which is provided on the second vacuum chamber side. Next, while pressurizing the first vacuum chamber, the molded body is pressed against the three-dimensional molded film using an elevating table, and the resin is stretched while stretching the three-dimensional molded film by utilizing the pressure difference between the two vacuum chambers. It is attached to the surface of the molded product. Finally, the resin molded product of the present invention can be obtained by opening the two vacuum chambers to atmospheric pressure and trimming the excess portion of the three-dimensional molded film as needed.

In the vacuum pressure bonding method, it is preferable to include a step of heating the three-dimensional molded film in order to soften the three-dimensional molded film and improve the moldability before the step of pressing the molded body against the three-dimensional molded film. .. The vacuum crimping method including this step may be particularly called a vacuum heating crimping method. The heating temperature in the step may be appropriately selected depending on the type of resin constituting the three-dimensional molded film, the thickness of the three-dimensional molded film, and the like, but even when a polyester resin film or an acrylic resin film is used as the base material. For example, it can usually be about 60 to 200 ° C.

In the resin molded product of the present invention, the molded resin layer may be formed by selecting a resin according to the intended use. The molding resin forming the molding resin layer may be a thermoplastic resin or a thermosetting resin.

Examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, ABS resins, styrene resins, polycarbonate (PC) resins, acrylic resins, vinyl chloride resins and the like. These thermoplastic resins may be used alone or in combination of two or more.

Examples of the thermosetting resin include urethane resin and epoxy resin. These thermosetting resins may be used alone or in combination of two or more.

In the first aspect, the transfer base material 3a is peeled off and removed from the resin molded product with the transfer base material obtained by integrating the three-dimensional molded film and the molding resin by the method as described above. , A resin molded product can be obtained. The step of peeling and removing the transfer base material 3a can be performed at any time, for example, the obtained resin molded product with the transfer base material can be taken out from the molding apparatus and at the same time the transfer base material 3a can be peeled off and removed. can. Further, in the resin molded product with a transfer base material, the transfer base material 3a serves as a protective sheet for the resin molded product, so that the resin molded product with a transfer base material is stored as it is without being peeled off after production. The transfer substrate may be peeled off at the time of use. By using it in such an embodiment, it is possible to prevent the resin molded product from being scratched due to rubbing during transportation or the like.

Since the resin molded product of the present invention has excellent scratch resistance and durability, for example, interior or exterior materials of vehicles such as automobiles; fittings such as window frames and door frames; buildings such as walls, floors and ceilings. Interior materials; housings for home appliances such as television receivers and air conditioners; can be used as containers and the like.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

(Example 1 and Comparative Examples 1 to 3)
[Manufacturing of 3D molded film]
As the transfer substrate, a polyethylene terephthalate film (thickness 50 μm) having an easy-adhesive layer formed on one surface was used. A release layer (thickness 1 μm) was formed by printing a coating liquid containing a melamine resin as a main component on the surface of the easy-adhesive layer of the polyethylene terephthalate film by gravure printing. Next, the ionizing radiation curable resin composition (EB-1 or EB-2) shown in Table 1 was applied onto the release layer with a barcoder so that the cured thickness was 5 μm. The coating film for forming the protective layer of No. 1 was formed. Further, in Example 1 and Comparative Example 3, the ionizing radiation curable resin composition (EB-1 or EB-2) shown in Table 1 is placed on the coating film so that the thickness after curing is 5 μm. Was coated with a bar coater to form a coating film for forming a second protective layer. Next, an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5Mrad) is irradiated from these coating films to cure the first protective layer forming coating film and the second protective layer forming coating film. The first protective layer and the second protective layer were formed. Next, a resin composition for forming a primer layer containing an acrylic polyol was applied on the first protective layer or the second protective layer by gravure printing to form a primer layer (thickness 1.5 μm). Further, a decorative layer is formed on the primer layer, which comprises an acrylic resin and a vinyl chloride-vinyl acetate-based copolymer resin as a binder resin (acrylic resin 50% by mass, vinyl chloride-vinyl acetate-based copolymer resin 50% by mass). A decorative layer (thickness 5 μm) of a hairline pattern was formed by gravure printing using a black-based ink composition for use. Further, Example 1 is obtained by forming an adhesive layer (thickness 4 μm) on the decorative layer by gravure printing using a resin composition for forming an adhesive layer containing an acrylic resin (softening temperature: 125 ° C.). In Comparative Example 3 and Comparative Examples 1 and 2, a three-dimensional molded film in which a transfer substrate / a release layer / a first protective layer / a second protective layer / a primer layer / a decorative layer / an adhesive layer are laminated in this order. Then, a three-dimensional molded film in which a transfer substrate / a release layer / a first protective layer / a primer layer / a decorative layer / an adhesive layer were laminated in this order was produced.

<Ionizing radiation curable resin composition>
EB-1: Caprolactone-based urethane acrylate (weight average molecular weight: 1900) 100 parts by mass (solid content 70%), isocyanate compound (HDI-based) 3.3 parts by mass (solid content 95%), ultraviolet absorber (Tinuvin 479) 1 part by mass, light stabilizer (LS-3410) 1 part by mass, EB-2: Polycarbonate urethane acrylate (weight average molecular weight: 22000) 100 parts by mass (solid content 25%), ultraviolet absorber (Tinuvin 479) 0.3 Parts by mass, 0.3 parts by mass of light stabilizer (LS-3410)

[Manufacturing of resin molded products]
Each of the three-dimensional molded films obtained above was placed in a mold so that the surface on the adhesive layer side faced the resin injection surface, the mold was closed, and the molten resin was injected into the mold. The molten resin was cooled, taken out from the mold, and the transfer base material and the release layer were peeled off to produce a resin molded product transferred so that the first protective layer was on the outermost surface. The temperature of the mold was set to 60 ° C, and the temperature of the molten resin was set to 265 ° C. The molten resin is obtained ^{by heating a mixed resin (CYCOLOY TM} Resin XCY620) of ABS resin and polycarbonate resin to 265 ° C. and melting the resin.

Scratch resistance evaluation The surface of the resin molded product was rubbed 10 times with a load of 0.5 kgf using steel wool (# 0000), and the surface was visually observed to evaluate the scratch resistance to steel wool according to the following criteria. The results are shown in Table 1.
A: The wound disappears in a few hours.
B: The wound disappears in 1 day.
C: The wound disappears in a few days.

Durability evaluation A (3 days)
The durability of the resin molded product obtained above was evaluated under the following conditions. The results are shown in Table 1. Using EYESUPERUVTESTER, ultraviolet rays of 365 nm and 60 mW / cm ² were irradiated for 20 hours per day, and then placed under dew condensation conditions for 4 hours, and this was repeated for 3 days (test period: 3 days). The changes in color and luster before and after the test were confirmed by Microgloss manufactured by BYK Gardner and CM-250 manufactured by Konica Minolta, and evaluated according to the following criteria. Further, the durability of the resin molded product after the test was evaluated from the viewpoint of peeling of the surface of the resin molded product by a grid tape test JIS K5400. The evaluation criteria are as follows. The results of each evaluation are shown in Table 1.
(Color evaluation)
A: The color difference ΔE before and after the test is within 3.
B: The color difference ΔE before and after the test exceeds 3.
C: The color difference ΔE before and after the test exceeds 3, and the color change can be easily discriminated visually.
(Evaluation of luster)
A: The gloss difference before and after the test is within 60 °.
B: The gloss difference before and after the test exceeds 60 °.
C: The gloss difference before and after the test exceeds 60 °, and the change in gloss can be easily discriminated visually.
(Evaluation of durability from the viewpoint of surface peeling)
A: No peeling on the surface of the resin molded product B: Peeling occurred on the surface area of the resin molded product of 30% or less C: Peeling occurred on the surface area of the resin molded product of more than 30%

Durability evaluation B (14 days)
In the durability evaluation A, the color, gloss change, and adhesion before and after the test were evaluated in the same manner as in the durability evaluation A, except that the test period was changed from 3 days to 14 days. The results of each evaluation are shown in Table 1.

As shown in Table 1, the resin molded product obtained by using the three-dimensional molded film of Example 1 includes a first protective layer and a second protective layer, and the first protective layer is caprolactone. It is formed of a cured product of an ionizing radiation curable resin composition (EB-1) containing a urethane (meth) acrylate, and the second protective layer is an ionizing radiation curable resin composition containing a polycarbonate (meth) acrylate. Since it is formed of the cured product of (EB-2), it is excellent in durability for a short period (3 days) and a long period (14 days) in addition to scratch resistance.

1 First protective layer 2 Second protective layer 3 Base material 3a Transfer base material 3b Laminating base material 4 Primer layer 5 Decorative layer 6 Transparent resin layer 7 Adhesive layer 8 Molding resin layer 10 Transfer layer

Claims (5)

It has at least a base material, a first protective layer, and a second protective layer in this order, and the base material can be peeled off from the first protective layer.
The first protective layer is formed of a cured product of an ionizing radiation curable resin composition containing caprolactone-based urethane (meth) acrylate.
The second protective layer is a three-dimensional molded film formed of a cured product of an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate. The three-dimensional molded film according to claim 1, wherein the thickness of the first protective layer and the thickness of the second protective layer are 1 to 10 μm, respectively. The three-dimensional molded film according to claim 1 or 2 , wherein at least one of the first protective layer and the second protective layer contains at least one of an ultraviolet absorber and a light stabilizer. The three-dimensional molded film according to any one of claims 1 to 3 , wherein the polycarbonate (meth) acrylate has a weight average molecular weight of 1000 to 50000. At least a molding resin layer, a second protective layer, a first protective layer, and a base material layer are provided in this order.
The base material can be peeled off from the first protective layer, and the base material can be peeled off from the first protective layer.
The first protective layer is formed of a cured product of an ionizing radiation curable resin composition containing caprolactone-based urethane (meth) acrylate.
The second protective layer is a resin molded product with a base material for transfer, which is formed of a cured product of an ionizing radiation curable resin composition containing polycarbonate (meth) acrylate.

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